Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures

The reaction of [AnCl(NR2)3] (An = U or Th; R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(C≡CH)(NR2)3] (1, An = U; 2, An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR2)3] results in the formation of [Na(TMEDA)][An(C≡CH)2(NR2)3] (4, An = U; 5, An = Th), which can be isolated in fair yields after workup. The reaction of 1 with 2 equiv of KC8 and 1 equiv of 2.2.2-cryptand in tetrahydrofuran results in formation of the uranium(III) acetylide complex [K(2.2.2-cryptand)][U(C≡CH)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(μ,η1:η1-C2)] (6, An = U; 7, An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2CH2)}(NR2)2] results in the formation of [U(NR2)3(μ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms in 2, 5, and 7 exhibit a characteristic spin-orbit-induced downfield shift, due to participation of the 5f orbitals in the Th-C bonds. Magnetism measurements demonstrate that 6 displays weak ferromagnetic coupling between the uranium(IV) centers (J = 1.78 cm-1).